Methanol → Dimethyl 4-nitro-1H-indene-2,2(3H)-dicarboxylate

HRID 2110133Notes

Reaction equation

HRID 2110133 reaction equation
CO.[H-].[Na+].[C:5]([O:12][CH3:13])(=[O:11])[CH2:6][C:7]([O:9][CH3:10])=[O:8].Br[CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[C:18]([N+:22]([O-:24])=[O:23])[C:17]=1[CH2:25]Br>CCOCC>[CH3:10][O:9][C:7]([C:6]1([C:5]([O:12][CH3:13])=[O:11])[CH2:25][C:17]2[C:16](=[CH:21][CH:20]=[CH:19][C:18]=2[N+:22]([O-:24])=[O:23])[CH2:15]1)=[O:8]

Participants

6

Reactant 4

HCID 887MethanolHCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 123177511,2-Bis(bromomethyl)-3-nitrobenzene

Product 1

HCID 57565181Dimethyl 4-nitro-1H-indene-2,2(3H)-dicarboxylateYield 70.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution stirred under nitrogen at room temperature, to 5.0 mL methanol in 15.0 mL ether was added 60% sodium hydride (0.84 g, 0.021 mol) in small portions. After the addition was complete, the nearly clear and colorless solution was stirred for 5 minutes. To it was then added 1.3 g dimethyl malonate, giving a slightly cloudy colorless solution. To this was rapidly added a suspension of 3.1 g 1,2-bis(bromomethyl)3-nitrobenzene, which immediate gave a precipitate suspended in a dark green solution. This was removed by filtation and the filtrate was concentrated. The residue was purified on silica (20%-100% CH2Cl2 in hexanes) to give 1.93 g off-white solid (67%).

Workup

  1. additionAfter the addition
  2. customgiving a slightly cloudy colorless solution
  3. additionTo this was rapidly added
  4. customimmediate gave a precipitate
  5. customThis was removed by filtation
  6. concentrationthe filtrate was concentrated
  7. customThe residue was purified on silica (20%-100% CH2Cl2 in hexanes)

Sources & evidence

ORD record
ord-585b6925639b4a31a076ae9a5b55e9be
Source dataset
uspto-grants-2009_04
Patent number
US07517884B2

Reaction notes

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